US9981903B2 - Method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds - Google Patents

Method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds Download PDF

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US9981903B2
US9981903B2 US15/651,105 US201715651105A US9981903B2 US 9981903 B2 US9981903 B2 US 9981903B2 US 201715651105 A US201715651105 A US 201715651105A US 9981903 B2 US9981903 B2 US 9981903B2
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alkyl
palladium
aryl
cycloalkyl
heteroaryl
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US20180022687A1 (en
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Kaiwu DONG
Ralf Jackstell
Matthias Beller
Dirk Fridag
Dieter Hess
Katrin Marie Dyballa
Frank Geilen
Robert Franke
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Evonik Operations GmbH
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B01J27/13—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/34—Esters of acyclic saturated polycarboxylic acids having an esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/44—Adipic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/349—1,2- or 1,4-additions in combination with further or prior reactions by the same catalyst, i.e. tandem or domino reactions, e.g. hydrogenation or further addition reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium

Definitions

  • the present invention relates to a novel method for preparing di- or tricarboxylic esters by alkoxycarbonylation of dienes having conjugated double bonds.
  • Dienes having conjugated double bonds (1,3-dienes), particularly 1,3-butadiene and isoprene, have diverse application in the chemical industry and serve for example as base material for preparing synthetic rubber.
  • a further promising application is the alkoxycarbonylation of 1,3-dienes to give dicarboxylic acids and the corresponding esters.
  • An alkoxycarbonylation is understood to mean the reaction of ethylenically unsaturated compounds such as dienes with carbon monoxide and alcohols in the presence of a metal or a metal complex and a ligand to give the corresponding esters.
  • the following scheme shows the general reaction equation of the alkoxycarbonylation of an ethylenically unsaturated compound.
  • 1,3-butadiene may be reacted to give dimethyl adipate for example, an important base material for nylon synthesis.
  • the synthesis of dimethyl adipate is accomplished in this case in two steps, wherein 1,3-butadiene is firstly reacted to give the ⁇ , ⁇ -unsaturated ester methyl 3-pentenoate, which is subsequently alkoxycarbonylated to give dimethyl adipate
  • 1,3-butadiene is firstly reacted to give the ⁇ , ⁇ -unsaturated ester methyl 3-pentenoate, which is subsequently alkoxycarbonylated to give dimethyl adipate
  • the object of the present invention is to provide a novel method for preparing di- or tricarboxylic esters, such as dimethyl adipate, with which high yields of the di- or tricarboxylic ester can be attained even in one reaction step.
  • process steps a), b), c) and d) can be effected in any desired sequence.
  • the addition of CO is effected after the co-reactants have been initially charged in steps a) to c).
  • Steps d) and e) can be effected simultaneously or successively.
  • CO can also be fed in two or more steps, in such a way that, for example, a portion of the CO is first fed in, then the mixture is heated, and then a further portion of CO is fed in.
  • (C 1 -C 12 )-alkyl encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C 1 -C 8 )-alkyl groups, more preferably (C 1 -C 6 )-alkyl, most preferably (C 1 -C 4 )-alkyl.
  • Suitable (C 1 -C 12 )-alkyl groups are especially methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-
  • the elucidations relating to the expression (C 1 -C 12 )-alkyl also apply in particular to the alkyl groups in —O—(C 1 -C 12 )-alkyl, —S—(C 1 -C 12 )-alkyl, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl and —N—[(C 1 -C 12 )-alkyl] 2 .
  • (C 3 -C 12 )-cycloalkyl encompasses mono-, bi- or tricyclic hydrocarbyl groups having 3 to 12 carbon atoms. Preferably, these groups are (C 5 -C 12 )-cycloalkyl.
  • the (C 3 -C 12 )-cycloalkyl groups have preferably 3 to 8, more preferably 5 or 6, ring atoms.
  • Suitable (C 3 -C 12 )-cycloalkyl groups are especially cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentadecyl, norbornyl, adamantyl.
  • (C 3 -C 12 )-heterocycloalkyl encompasses nonaromatic, saturated or partly unsaturated cycloaliphatic groups having 3 to 12 carbon atoms, where one or more of the ring carbon atoms are replaced by heteroatoms.
  • the (C 3 -C 12 )-heterocycloalkyl groups have preferably 3 to 8, more preferably 5 or 6, ring atoms and are optionally substituted by aliphatic side chains.
  • the heterocycloalkyl groups as opposed to the cycloalkyl groups, one or more of the ring carbon atoms are replaced by heteroatoms or heteroatom-containing groups.
  • heteroatoms or the heteroatom-containing groups are preferably selected from O, S, N, N( ⁇ O), C( ⁇ O), S( ⁇ O).
  • a (C 3 -C 12 )-heterocycloalkyl group in the context of this invention is thus also ethylene oxide.
  • Suitable (C 3 -C 12 )-heterocycloalkyl groups are especially tetrahydrothiophenyl, tetrahydrofuryl, tetrahydropyranyl and dioxanyl.
  • (C 6 -C 20 )-aryl encompasses mono- or polycyclic aromatic hydrocarbyl radicals having 6 to 20 carbon atoms. These are preferably (C 6 -C 14 )-aryl, more preferably (C 6 -C 10 )-aryl.
  • Suitable (C 6 -C 20 )-aryl groups are especially phenyl, naphthyl, indenyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl, pyrenyl, coronenyl.
  • Preferred (C 6 -C 20 )-aryl groups are phenyl, naphthyl and anthracenyl.
  • (C 3 -C 20 )-heteroaryl encompasses mono- or polycyclic aromatic hydrocarbyl radicals having 3 to 20 carbon atoms, where one or more of the carbon atoms are replaced by heteroatoms. Preferred heteroatoms are N, O and S.
  • the (C 3 -C 20 )-heteroaryl groups have 3 to 20, preferably 6 to 14, particularly preferably 6 to 10 ring atoms.
  • Suitable (C 3 -C 20 )-heteroaryl groups are especially furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.
  • halogen especially encompasses fluorine, chlorine, bromine and iodine. Particular preference is given to fluorine and chlorine.
  • the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 in the case that these are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl, may be each substituted independently of one another by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )
  • the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 in the case that these are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl, may be each substituted independently of one another by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —(C 6 -C 20 )
  • the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 if they are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl, may be each independently of one another substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl.
  • the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 if they are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl, may be each independently of one another substituted by one or more substituents selected from —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl.
  • the radicals R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are unsubstituted if they are —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 3 -C 20 )-heteroaryl.
  • R 1 , R 2 , R 3 , R 4 are selected from —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 20 )-heteroaryl; particularly preferably from —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 20 )-heteroaryl.
  • R 1 , R 2 , R 3 , R 4 are in each case —(C 6 -C 20 )-aryl.
  • R 1 , R 2 , R 3 , R 4 may be substituted as described above.
  • R 1 , R 2 , R 3 , R 4 are in this case preferably unsubstituted.
  • R 5 , R 6 are selected from —H, —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl; particularly preferably from —H, —(C 1 -C 12 )-alkyl. Most preferably, R 5 , R 6 are each —H. In this case, R 5 , R 6 , if they are —(C 1 -C 12 )-alkyl or —(C 6 -C 20 )-aryl, are substituted as described above. However, R 5 , R 6 are preferably unsubstituted if they are —(C 1 -C 12 )-alkyl or —(C 6 -C 20 )-aryl.
  • the phosphine ligand is a compound according to formula (1):
  • the diene used as reactant in the method according to the invention comprises at least two conjugated double bonds.
  • the diene may be substituted by one or more alkyl, alkenyl, alkynyl or aryl groups.
  • the diene preferably comprises a total of 4 to 30 carbon atoms, preferably 4 to 22 carbon atoms, most preferably 4 to 12 carbon atoms.
  • the diene may also comprise more than two double bonds, wherein two of them must be conjugated.
  • the diene comprises three or more double bonds, it has been shown that it can even be converted directly to a tricarboxylic ester in the reaction according to the invention. Therefore, the reaction according to the invention also comprises the conversion of the diene to a tricarboxylic ester.
  • the diene may comprise additional functional groups.
  • the diene comprises one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, hydroxyl, sulphhydryl, amino, ether, thioether, aryl, heteroaryl or silyl groups and/or halogen substituents.
  • the diene does not comprise any of these functional groups.
  • Suitable dienes are in particular 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene, 7-methyl-3-methylene-1,6-octadiene (myrcene) or 2-phenyl-1,3-butadiene.
  • the diene is selected from compounds of the formula (II)
  • R 7 , R 8 , R 9 , R 10 may each independently be selected from —H, —(C 1 -C 12 )-alkyl and —(C 6 -C 20 )-aryl. Particularly preferably, R 7 , R 8 , R 9 , R 10 are independently selected from —H, —(C 1 -C 6 )-alkyl and phenyl. Most preferably, R 7 , R 8 , R 9 , R 10 are each independently selected from —H, methyl, ethyl and phenyl.
  • the radicals R 8 , R 9 are preferably —H.
  • the radicals R 8 , R 9 , R 10 are particularly preferably —H.
  • the diene is selected from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,4-dimethyl-1,3-pentadiene or 2-phenyl-1,3-butadiene. Most preferably, the diene is isoprene.
  • the alkoxycarbonylation according to the invention is catalysed by a Pd complex.
  • the Pd complex is in this case formed in situ from a compound comprising Pd, and the free phosphine ligand.
  • the compound comprising Pd is also referred to as catalyst precursor.
  • the catalyst precursor is selected from palladium dichloride (PdCl 2 ), palladium dibromide (PdBr 2 ), palladium diiodide (PdI 2 ), palladium(II) acetylacetonate [Pd(acac) 2 ], palladium(II) acetate [Pd(OAc) 2 ], bis(dibenzylideneacetone)palladium [Pd(dba) 2 ], bis(acetonitrile)dichloropalladium(II) [Pd(CH 3 CN) 2 Cl 2 ], palladium (cinnamyl) dichloride [Pd(cinnamyl)Cl 2 ].
  • the catalyst precursor is preferably selected from palladium dichloride (PdCl 2 ), palladium dibromide (PdBr 2 ), palladium diiodide (PdI 2 ), palladium(II) acetylacetonate [Pd(acac) 2 ], palladium(II) acetate [Pd(OAc) 2 ], bis(dibenzylideneacetone)palladium [Pd(dba) 2 ].
  • the catalyst precursor is particularly preferably selected from palladium dichloride (PdCl 2 ), palladium dibromide (PdBr 2 ) and palladium diiodide (PdI 2 ). Most preference is given to palladium dibromide (PbBr 2 ).
  • the alcohol in method step c) comprises preferably 1 to 30 carbon atoms, more preferably 1 to 22 carbon atoms, especially preferably 1 to 12 carbon atoms.
  • the alcohol may be, for example linear, branched, alicyclic or cyclic.
  • the alcohol may also comprise unsaturated or aromatic groups.
  • the alcohol may comprise one or more hydroxyl groups.
  • the alcohol may, in addition to the one or more hydroxyl groups, contain further functional groups.
  • the alcohol may additionally comprise one or more functional groups selected from carboxyl, thiocarboxyl, sulpho, sulphinyl, carboxylic anhydride, imide, carboxylic ester, sulphonic ester, carbamoyl, sulphamoyl, cyano, carbonyl, carbonothioyl, sulphhydryl, amino, ether, thioether or silyl groups and/or halogen substituents.
  • the alcohol does not comprise any further functional groups except for hydroxyl groups.
  • the alcohol comprises only one hydroxyl group.
  • Suitable alcohols are, for example, alkanols or cycloalkanols, particularly methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexanol, isononanol, 2-propylheptanol.
  • alkanols or cycloalkanols particularly methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexan
  • Suitable alcohols are also aryl-substituted alkanols such as, e.g. benzyl alcohol, 1-phenylethanol or 2-phenylethanol.
  • Suitable alcohols having more than one hydroxyl group are, for example, cyclohexane-1,2-diol, 1,2-ethanediol, 1,3-propanediol, glycerol, 1,2,4-butanetriol, 2-hydroxymethyl-1,3-propanediol, 1,2,6-trihydroxyhexane, pentaerythritol, 1,1,1-tri(hydroxymethyl)ethane, catechol, resorcinol and hydroxyhydroquinone.
  • Suitable alcohols are also sucrose, fructose, mannose, sorbose, galactose and glucose.
  • the alcohol in method step c) is selected from methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, cyclohexanol, 2-ethylhexanol, isononanol, 2-propylheptanol, benzyl alcohol, 1-phenylethanol or 2-phenylethanol.
  • the alcohol in method step c) is preferably selected from methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or 2-phenylethanol.
  • the alcohol in method step c) is particularly preferably selected from methanol, ethanol, isopropanol, n-butanol or 2-phenylethanol.
  • the alcohol in method step c) is methanol.
  • the alcohol in method step c) is used in excess.
  • the alcohol in method step c) is used simultaneously as solvent.
  • a further solvent is used, selected from, for example: toluene, xylene, hexane, heptane, tetrahydrofuran (THF) or methylene chloride (CH 2 Cl 2 ).
  • Particularly preferred solvents are toluene and xylene (particularly p-xylene).
  • CO is fed in step d) preferably at a partial CO pressure between 0.1 and 10 MPa (1 to 100 bar), preferably between 1 and 8 MPa (10 to 80 bar), particularly preferably between 3 and 6 MPa (30 to 60 bar), most preferably between 3.5 and 4.5 MPa (35 to 45 bar).
  • the reaction mixture is heated in step e) of the method according to the invention preferably to a temperature between 10° C. and 180° C., more preferably between 20 and 160° C., particularly preferably between 80 and 160° C., most preferably between 130 and 150° C., in order to convert the diene to a di- or tricarboxylic ester.
  • the molar ratio of the diene initially charged in step a) to the alcohol added in step c) is preferably between 1:1 and 1:20, more preferably 1:2 to 1:10, especially preferably 1:3 to 1:4.
  • the mass ratio of Pd to the diene initially charged in step a) is preferably between 0.001% and 0.5% by weight, more preferably between 0.01% and 0.1% by weight, especially preferably between 0.01% and 0.05% by weight.
  • the molar amount of Pd is preferably between 0.1 and 10 mol %, preferably 0.5 to 5 mol %, particularly preferably 0.8 to 2 mol %.
  • the molar ratio of the phosphine ligand to Pd is preferably between 0.1:1 and 400:1, more preferably between 0.5:1 and 400:1, especially preferably between 1:1 and 100:1, most preferably between 2:1 and 50:1.
  • the method is conducted with addition of an acid.
  • the method therefore additionally comprises step c′): adding an acid to the reaction mixture.
  • This may preferably be a Br ⁇ nsted or Lewis acid.
  • Suitable Br ⁇ nsted acids preferably have an acid strength of pK a ⁇ 5, more preferably an acid strength of pK a ⁇ 3.
  • the reported acid strength pK a is based on the pK a determined under standard conditions (25° C., 1.01325 bar).
  • the acid strength pKa in the context of this invention relates to the pKa of the first protolysis step.
  • the acid is not a carboxylic acid.
  • Suitable Br ⁇ nsted acids are, for example, perchloric acid, sulphuric acid, phosphoric acid, methylphosphonic acid and sulphonic acids.
  • the acid is sulphuric acid or a sulphonic acid.
  • Suitable sulphonic acids are, for example, methanesulphonic acid, trifluoromethanesulphonic acid, tert-butanesulphonic acid, p-toluenesulphonic acid (PTSA), 2-hydroxypropane-2-sulphonic acid, 2,4,6-trimethylbenzenesulphonic acid and dodecylsulphonic acid.
  • Particularly preferred acids are sulphuric acid, methanesulphonic acid, trifluoromethanesulphonic acid and p-toluenesulphonic acid.
  • a Lewis acid used may, for example, be aluminium triflate.
  • the amount of acid added in step c′) is 0.3 to 40 mol %, preferably 0.4 to 15 mol %, particularly preferably 0.5 to 5 mol %, most preferably 0.6 to 3 mol %, based on the molar amount of the diene initially charged in step a).
  • relative molar amounts in mol % refer to the molar amount of olefin (substrate).
  • a 4 ml sample vial was charged with PdBr 2 (2.64 mg, 1.0 mol %), PTSA (9.5 mg, 5.0 mol %), the respective ligand (2.0 mol %) and a magnetic stirrer bar.
  • the vial was sealed with a septum (PTFE-coated styrene-butadiene rubber) and a phenol resin cap. Gas exchange between sample vial and environment was enabled by means of a cannula pierced through the septum.
  • the sample vial was purged three times with argon.
  • ligand 1 used according to the invention as sole ligand investigated, is capable of converting isoprene in one step to a dicarboxylic acid.
  • ligands 2 to 4 described in the prior art in the context of alkoxycarbonylation of isoprene cf. X. Fang et al, Angew. Chem. Int. Ed., 2014, 53, 9030-9034
  • monoesters but no dicarboxylic esters are obtained.
  • a 4 ml sample vial was charged with 1.0 mol % or 0.5 mol % of the respective catalyst precursor, PTSA (9.5 mg, 5.0 mol %), ligand 1 (11.6 mg, 2.0 mmol %) and a magnetic stirrer bar.
  • the vial was sealed with a septum (PTFE-coated styrene-butadiene rubber) and a phenol resin cap. Gas exchange between sample vial and environment was enabled by means of a cannula pierced through the septum.
  • the sample vial was purged three times with argon.
  • Example Catalyst precursor Yield 3a Yield 4a 1 1.0 mol % PdCl 2 71% 26% 2 1.0 mol % PdBr 2 89% 11% 3 1.0 mol % PdI 2 67% 19% 4 1.0 mol % Pd(OAc) 2 41% 32% 5 1.0 mol % Pd(acac) 2 44% 27% 6 0.5 mol % Pd 2 (dba) 3 24% 52%
  • a 4 ml sample vial was charged with PdBr 2 , PTSA, ligand 1 in the amount specified and a magnetic stirrer bar.
  • the vial was sealed with a septum (PTFE-coated styrene-butadiene rubber) and a phenol resin cap. Gas exchange between sample vial and environment was enabled by means of a cannula pierced through the septum.
  • the sample vial was purged three times with argon.
  • Para-xylene (2.0 ml), 1.0 mmol of diene and 3.0 mmol of alcohol were injected into the sample vial by means of a syringe.
  • the sample vial was placed on a metal plate and this was transferred under an argon atmosphere into a 300 ml autoclave of the 4560 type from Parr Instruments. After the autoclave had been purged three times with CO, the CO pressure was adjusted to 40 bar at room temperature. The reaction ran for 48 or 96 hours at 140° C. After completion of the reaction, the autoclave was cooled to room temperature and carefully decompressed. Isooctane (100 ⁇ l) was added as internal GC standard. The yield of the main product was determined by means of GC analysis. The results are compiled in the following table.
  • Example 1 Diene Alcohol Main product Yield 1 Isoprene Methanol 76% 2 Isoprene Ethanol 82% 3 Isoprene Isopropanol 70% 4 Isoprene n-Butanol 94% 5 Isoprene 2-Phenylethanol 94% 6 n-Butanol 79% 7 n-Butanol 99% 8 n-Butanol 30% 9 n-Butanol 37% 1) examples 1 to 5, 7 and 8: 1.0 mol % PdBr 2 , 2.0 mol % ligand 1, 5.0 mol % PTSA, 48 h; examples 6 and 9: 2.0 mol % PdBr 2 , 4.0 mol % ligand 1, 10.0 mol % PTSA, 96 h.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4792620A (en) * 1983-10-14 1988-12-20 Bp Chemicals Limited Carbonylation catalysts
US20060235241A1 (en) 2003-05-22 2006-10-19 Eit Drent Process for the carbonylation of a conuugated diene
US20090131630A1 (en) * 2005-02-11 2009-05-21 Van Broekhoven Johannes Adrian Process For the Preparation of a Dicarboxylic Acid
US20170022234A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Phosphine ligand and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW524801B (en) * 1999-03-22 2003-03-21 Shell Int Research Process for the carbonylation of conjugated dienes
GB201000078D0 (en) * 2010-01-05 2010-02-17 Lucite Int Uk Ltd Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands
US9376365B2 (en) * 2012-11-23 2016-06-28 Firmenich Sa Hydrocarbonylation or methoxycarbonylation of 1,3-diene derivatives with palladium complex

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4792620A (en) * 1983-10-14 1988-12-20 Bp Chemicals Limited Carbonylation catalysts
US20060235241A1 (en) 2003-05-22 2006-10-19 Eit Drent Process for the carbonylation of a conuugated diene
US20090131630A1 (en) * 2005-02-11 2009-05-21 Van Broekhoven Johannes Adrian Process For the Preparation of a Dicarboxylic Acid
US20170022234A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Phosphine ligand and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds
US20170022137A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Benzene-based diphosphine ligands for alkoxycarbonylation
US20170022138A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Butyl-bridged diphosphine ligands for alkoxycarbonylation
US20170022139A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Monophosphine compounds and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds
US20170022235A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Ferrocene-based compounds and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds
US20170022236A1 (en) 2015-07-23 2017-01-26 Evonik Degussa Gmbh Ferrocene-based compounds and palladium catalysts based thereon for the alkoxycarbonylation of ethylenically unsaturated compounds

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
European Search Report dated Jan. 11, 2017 for EP 16 18 0048 (1 page).
Fang et al, Angewandte Chemie International Edition, Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes under Acid-Free Conditions: Atom-Economic Synthesis of b,g-Unsaturated Esters. 2014, 53, pp. 9030-9034. *
Fang, X., Li, H., Jackstell, R. and Beller, M. (2014), Palladiurn-catalyzed alkoxycarbonylation of conjugated diener under acid-free conditions: Atom-economic synthesis of β,γ-unsaturated esters. Angew. Chem. Int. Ed., 53: 9030-9034.
Norskov et al, Nature Chemistry, Towards the Computational Design of Solid Catalysts, 2009, 1, pp. 37-46. (Year: 2009). *
U.S. Appl. No. 15/649,743, filed Jul. 14, 2017, Dong, et al.
U.S. Appl. No. 15/649,759, filed Jul. 14, 2017, Dong, et al.
U.S. Appl. No. 15/649,770, filed Jul. 14, 2017, Dong, et al.
U.S. Appl. No. 15/649,781, filed Jul. 14, 2017, Dong, et al.
U.S. Appl. No. 15/651,042, filed Jul. 17, 2017, Fang, et al.
U.S. Appl. No. 15/651,062, filed Jul. 17, 2017, Dong, et al.
U.S. Appl. No. 15/651,169, filed Jul. 17, 2017, Dong, et al.

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